Phthalic acid hair spray



i 4% i i matted 3,234,098 liTl-lALZ'C ACID HAIR SF'RAY li'eiarieh Sender, Wieshaden-liiebri z, and Heinz Lulteseli, llltillililfgfi *1. Germany, ass goers to Chemisehe W -Hie "K imt, Wirah:uleit-Eiieltriuh, Germany, a eorpw ration of Ge tauy No Dra'tving. Filed May 31, 1963, Ser. No. 234,319

Ciafms priority, appiieation Germany, June 1, 1952,

6 27,231; Dec. 15, ram, 0 28,675 8 Claims. (Cl. 167-87.l)

This invention is concerned with improvements in or relating to hair sprays.

It has been proposed to use water-soluble synthetic resins, e.g. half esters of copolymers of maleic anhydride, condensation products of formaldehyde with hydantoin substituted in the -position, N-vinyl-Z-oxazolidone polymcrs, polymers of N-vinylpyrrolidone or its copolymers with vinyl acetate, polyvinylimidazole and panthenol in aerosol hair sprays.

These water-soluble synthetic resins effect a sufi'icient still'ening of the hair and impart gloss to it. They have however the important disadvantage that in the case of slightly greasy hair this looks unsightly and forms locks and when used in conjunction with water waves (waves prepared with the aid of water) these sag if the air i too humid.

It has been proposed to use water-insoluble resins, namely those which have been obtained by esterificatien of phthalic anhydride with pentacrythritol in aerosol hair sprays. These resins are however neither soluble in nor compatible with fats, so that that in most cases they are not able to absorb the grease produced by the scalp and the gloss of the hair is lost because the surface of the hair becomes uneven.

We have now surprisingly found that certain polyester resins do not have these disadvantages and may be used to yield hair sprays which absorb grease excellently. Since they also forman even surface on the single hairs, even with very greasy hair, they impart a very good gloss to the treated hair. Due to their good fat solubility and fat compatibility it is also possible to use fatty substances in the hair sprays and thus produce very suitable hair sprays for dry hair. Moreover, the resins are odorless, clear and physiologically inert.

According to the invention there is provided a composition suitable for use as a hair spray comprising a synthetic resin of a melting point about 40 C. functioning as a hair setting compound, said synthetic resin being an esterification product of a phthalic acid (or an anhydride where such exists) and a dihydric alcohol, and a propellant and/or a perfume. The said dihydric alcohol is an alkane diol of 2 to 6 carbon atoms, an ether of a polyhydrie alcohol having 3 to 6 hydroxy groups, in which the hydroxy groups in excess of two are ctherified by alkyl groups of l to 3 carbon atoms, 4,4-clihydroxydicyclohexylpropane or a mixture of any one of the aforementioned alcohol components with less than an equivalent amount with respect to the latter of a polyhydric alcohol containing at least 3 and at most 6 hydroxy groups.

The propellant is preferably a fiuorohydrocarbon or a chlorofiuorohydrocarbon in which even all of the hydrogen atoms may be substituted by halogen atoms, particularly the variou chlorofiuoromethanes. As propellant there is also suitable octafluorocyclobutane, if desired in admixture with isobutane, the proportion of which in the mixture may be between and 33%.

The synthetic resin may be produced by reaction of the above-mentioned acids with the above-mentioned dihydric alcohols, for example in an equivalent ratio from 1:09 to 1:1.4, preferably from 1:1 to 1:1.25. In general the esterification is preferably carried out until the resin has an acid value from so to 150, mtvtu'itageously from 90 to 120. Such resins should be hard and non-tacky; thus they should have a melting point above 40 C., preferably above C. In general they are distinguished by a good solubility in halogen-containing, especially chlorine-containing hydrocarbons, such as methylene chloride, and generally also in lower and higherhlcohols.

The dihydric alcohol component of the resin preferably contains at least three carbon atoms bound to each other by carbon to carbon bonds. The alcohol component may be, for example, ethylene glycol, propanodiol-l,2 or -l,3, butanediol-l,3 or butancdiol-1,4, hexanediol-2,5, hcxcnediol-1,6 or a mixture of such alcohols, but preferably it is 2,2-dimethyl propanediol-1,3 or 4,4-dihydroxy-dicyclohexylpropane. Homologues of this last-mentioned substance may also be used. As aleohol component there may also be used ethers of polyhydric alcohols in which the hydroxy groups in excess of 2 are etherified by shortchaincd aliphatic radicals such as methyl, ethyl, propyl or isopropyl but which others still contain 2 free hydroxy groups. According to a further preferred embodiment the synthetic resins may be modified inasmuch as the alcohol component used is a mixture of a dihydric alcohol with less than an equivalent portion with respect to the latter of a polyhydric alcohol containing at least 3 hydroxyl groups e.g. glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol or mannitol. The polyhydric alcohol may be used in such modified polyester resins, for example in an amount up to 80 equivalent percent, preferably between and equivalent percent, calculated on the dihydric alcohol.

In addition to the synthetic resin the hair sprays according to the invention may also contain additives such as solvents and diluents.

Of course, in all instances mixtures of several compounds may be used instead of a single compound.

In order that the invention may be well understood the following examples are given by way of illustration only. In the examples parts are by weight unless otherwise stated.

Example 1 (a) A fat-free hair spray can be obtained by mixing the following raw materials to form a base:

Parts Synthetic resin prepared from 1 equivalent phthalie anhydride, about 0.7 equivalent 2,2-dimethyl- 1 .3-propanediol and about 0.4 equivalent pentaerythritol '(acid value 100-110, melting point 45-50 C.) 2.50 Triethylcitrate 0.30 Perfume 0.50 Methylene chloride 30.00 Isopropanol 66.70

(b) This base in admixture with a propellant is used to fill aerosol containers in the following proportion and order:

Parts Base Propellant (monofluorotrichloromethanc:difluorodichloromethane 37:63 75 Example 2 prising a carricr and an ellcctivc amount of a synthetic A {any hair spray can be obtained from the fonowing resin with a melting point above 40 and an acid numcom 6 her between 80 and 150 and functioning as a hair setting p n nts. B compound, said synthetic resin being an cstcrification S h Paris product of an unsubstituted phthalic acid and a dihydric I (sec Example?) alcohol selected from the group consisting of (1) an s'oprfipylmynsmte alkane diol of 2 to 6 carbon atoms, (2) ethers of oly '5 hydric alcohols having 3 to 6 hydroxy groups and in NE" Which the hydroxy groups in excess of two are etherified I chlondc 30-00 by alkyl radicals of 1 to 3 carbon atoms, (3) 4,4'-clil1y Sopropanol 64-70 droxydicyelohexyl; in and (4) mixtures of any one of components 1 to j l less than an equivalent amount; mO'OO with respect to the hitter of a polyhyclric alcohol con (1 contents f l; Part5 tarning at least 3 and at most 6 hydroxy groups, the: B 30 acid and the alcohol c mponents being contained in the: Propellant (see Example 1) 75 Said resin in an equivalent ratio between 1:09 and l:l.4.. Example 3 2. A composition as claimed in claim 1, wherein thepolyhydric alcohol is pentaerythritol. in a similar manner to Examples 1 and 2 other polyesters 3. A composition as claimed in claim 1, wherein said also can be used which have been prepared from: polyhydric alcohol component is used in the resin in an (a) parts of phthalic acid, amount in the range from 50-7 equivalent percent a calculated on the amount of drhydric alcohol. ([2) parts of pcntacrythrnol, and

V 4. A composition suitable for use as a hair spray com- (cl) 40 parts of ethylene g1; col, or 0 prising a synthetic resin of a melting point above 4-0 C. (02) parts of propanediol 1,2, or r g f a l u d (C3) parts of butancdiomg or 20 up to 8 3 C. uncttontn as aaair so mg compo n san synthetic resin being an estertficatlon product of at least (04) 157 parts of 4,4'-dihydroxydicyclohexylpropane. l

These polyester resins have the following characteristic one 161d Component Selene? from l p 1 1; v lu of phthalic acid and phthahc anhydride with 4,4'-dihy- Melting ran c C. 40/51 52/58 5 /5 /83. Aci lvulucfuinui -105 -110 3 9 -125.

Yistr'osityol a mixtrllrc with the same amopat o nthy cue glyco monocthylcther at 20 (in en). 124 15L lli' 1&0. Solubility in ethyl alcohol Ncalrly 1tn- Until l:l.5- Until AS s so til) 0. Solubility in methylene chloride As desircd As dcsircd As dcsirod As desired.

droxydicyclohexylpropane and 50 to 75 equivalent percent, calculated on the amount of dihydric alcohol, of pentaerythrttol, said esterification product containing the acid Resins cl and c4 were, for example, manufactured according to the following formulations.

(a) or c4 igs n the al hol component in an equivalent raito between hopropylmyrismte 1'50 45 111 and 1-2 nd having an acid number betwccn 90 and Pummn on 500 n s i hair spray composition also containin a Lanolin refinery product 0.50 X and a 9 Perfume 0.50 o posit on suitable for use as a harr spray com- Mcthylcnc Chloride 40.00 p js nc l nvc am ount of a synthetic resin with a isopropanol 4970 50 f g n rm be c 40 C. up to about 83 C. functionmg as a hair setting compound, said synthetic resin ing 10000 an1 eitriiritficatiortih oduct of least ofne hatfidrcomppnen se ece rom e group consisting o tta lC acic an The Pmamn 011 used was clear nearly colorless and phtl' lic anhydride with at least one dii'iydric alcohol se lected from the group consisting of (1) an alkane diol of odorless and had a viscosity of 3-5 cp. The lanolin re- 2 to 6 carbon atoms, (2) ethers of polyhydric alcoholsfinery product was a solid, slightly yellowish wax-like material of the dropping point 59-70 C., which only con- V H v J tained lanolin fraction-s soluble in cold ethanol, did not hfwmg to 6 groups i m whlch the hymmy ha e m un le'lsant Odor and had a saponification groups in excess of two are ctherificd by alkyl radicals of p 1 to 3 carbon atoms, and (3) 4,4-dihydroxydicyclohcx- 05210 ylpropane, and (4) mixtures of any one of components The mxmre if viascfined aerosol containers m 60 l to 3 with less than an equivalent amount with respect the manner dcscnbcdm to the latter of a polyhydric alcohol containing at least (b) Non-fatty hair spray: Parts 3 and at most 6 hydroxy groups, and a propellant com Synthetic resin cl or c4 prising a halogenated hydrocarbon, said halogens being: Acetylbutylcitrate 0- 65 selected from the group consisting of (A) fluorine and Dimcthylphthalate (B) fluorine and chlorine, the acid and the alcohol com- Perfume 050 ponents being contained in the said resin in an equivalent Isopropa'uol 66-50 ratio between 1:09 and 121.4.

30-00 6. A composition suitable for use as a hair spray com- Methylenc chloride 70 prising a carrier and an effective amount of a synthetic 100-00 resin with a melting point above 40 C. up to about 83 C. functioning as a hair setting compound, saiu synthetic The mixture (b) was filled into aerosol containers in p the manner described in Example 1 resin being an esterification product of at least one acid What is claimed is: component selected from the group consisting of phthalic 75 acid and phthalic anhydride with at least one dihydric 1. A composition suitable for use as a hair spray comalcohol selected from the group consisting of (1) an alkanc (liol of 2 to 6 carbon atoms, (2) others of polyhydric alcohols having 3 to 6 hydroxy groups and in which the hydroxy groups in excess of two are etherificd by alkyl radicals of 1 to 3 carbon atoms, (3) 4,4dihydroxydicyclohexylpropanc, and (4) mixtures of any one of componcnts l to 3 with less than an equivalent amount with respect to the latter of a polyhydric alcohol containing at least 3 and at most 6 hydroxy groups, the acid and the alcohol components being contained in the synthetic resin in an equivalent ratio between 1:1 and 1:125 and the synthetic resin having an acid number between 90 and 120.

7. A composition as claimed in claim 1. wherein the carrier is a propellant and wherein the synthetic resin has a melting point above C. and the alcohol component thereof contains at least 3 carbon atoms.

8. A composition suitable for use as a hair spray comprising a synthetic resin with a melting point above 40 C. up to about 83 C. functioning as a hair setting compound, said synthetic resin being an esterification prodnet of at least one acid component selected from the group consisting of phthalic acid and phthalic anhydridc with 2,2-dimethyl-1,3-propanediol and to equivalent perccnt, calculated on the amount of dihydric alcohol, of pcntacrythritol, said estcrification product containing the acid and the alcohol component in an equivalent ratio between 1:1 and 121.25 and having an acid number between and 120. and said hair spray composition also containing a perfume and a propellant.

References Cited by the Examiner UNITED STATES PATENTS 2,465,319 3/1949 Whinfield et a1 260=-75 2,752,320 6/1956 Dewitt 260--33.8 2,957,838 10/1960 Mills 16787.2

JULIAN S. LEVITI, Primary Examiner.

FRANK CACCIAPAGLIA, 1a., VERA C. CLARKE,

Examiners. 

4. A COMPOSITION SUITABLE FOR USE AS A HAIR SPRAY COMPRISING A SYNTHETIC RESIN OF A MELTING POINT ABOVE 40*C. UP TO 83*C. FUNCTIONING AS A HAIR SETTING COMPOUND, SAID SYNTHETIC RESIN BEING AN ESTERIFICATION PRODUCT OF AT LEAST ONE ACID COMPONENT SELECTED FROM THE GROUP CONSISTING OF PHTHALIC ACID AND PHTHALIC ANHYDRIDE WITH 4,4''-DIHYDROXYDICYCLOHEXYLPROPANE AND 50 TO 75 EQUIVALNET PERCENT, CALCULATED ON THE AMOUNT OF DIHYDRIC ALCOHOL, OF PENTAERYTHRITOL, SAID ESTERIFICATION PRODUCT CONTAINING THE ACID AND THE ALCOHOL COMPONENT IN AN EQUIVALENT RATIO BETWEEN 1:1 AND 1:1.25 AND HAVING AN ACID NUMBER BETWEEN 90 AND 120, AND SAID HAIR SPRAY COMPOSITION ALSO CONTAINING A PERFUME AND A PROPELLANT. 